TW201409486A - Conductive composition for collector electrode of solar cell and solar cell unit - Google Patents

Conductive composition for collector electrode of solar cell and solar cell unit Download PDF

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TW201409486A
TW201409486A TW101130260A TW101130260A TW201409486A TW 201409486 A TW201409486 A TW 201409486A TW 101130260 A TW101130260 A TW 101130260A TW 101130260 A TW101130260 A TW 101130260A TW 201409486 A TW201409486 A TW 201409486A
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solar cell
conductive composition
forming
silver salt
epoxy resin
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TW101130260A
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Chinese (zh)
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Nao Sato
Kazunori Ishikawa
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Yokohama Rubber Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The present invention provides a conductive composition for collector electrode of solar cell and solar cell unit by using the composition capable of forming electrode with excellent adhesion for silicon substrate or TCO, wherein conductive composition for collector electrode of solar cell comprises silver powder (A) and silane compound (B) shown by the following equation (I) ( where R1 and R2 represent Alkylation respectively, R3 represents 2 valence paraffin with hetero atom, m represents an integer between 1 and 3, multiple R1s and R2s can be identical or different).

Description

太陽能電池集電電極形成用導電性組成物及太陽能電池單元 Conductive composition for forming solar cell collector electrode and solar cell unit

本發明為關於太陽能電池集電電極形成用導電性組成物與太陽能電池單元。 The present invention relates to a conductive composition for forming a current collector electrode for a solar cell and a solar battery cell.

以往已知下述製造電路基板之方法：將由銀粒子等之導電性粒子中添加並混合由熱塑性樹脂(例如，丙烯酸樹脂、醋酸乙烯樹脂等)或熱固化性樹脂(例如，環氧樹脂、不飽和聚酯樹脂等)形成之黏結劑、有機溶劑、固化劑、觸媒等而得到之銀膏(導電性組成物)依既定之電路圖案印刷在合成樹脂基材上(例如，聚酯薄膜等)，並對這些進行加熱而形成呈導體電路之導電性配線。 In the prior art, a method of manufacturing a circuit board is known, in which conductive particles such as silver particles are added and mixed with a thermoplastic resin (for example, an acrylic resin, a vinyl acetate resin, or the like) or a thermosetting resin (for example, an epoxy resin, A silver paste (conductive composition) obtained by forming a binder, an organic solvent, a curing agent, a catalyst, or the like, which is formed by a saturated polyester resin or the like, is printed on a synthetic resin substrate in accordance with a predetermined circuit pattern (for example, a polyester film, etc.) And heating these to form a conductive wiring in a conductor circuit.

例如，在專利文獻1中記載有如下內容：“一種導電膏，其特徵為，導電粒子、溶劑、黏結劑樹脂以及相對於導電性粒子100重量份以SiO2換算後為0.1~3重量份之四氧烷基矽烷的部分水解縮合物。”(「請求項1」)；銀粒子作為導電微粒子(「請求項4」)。 For example, Patent Document 1 discloses a conductive paste characterized in that the conductive particles, the solvent, the binder resin, and the conductive particles are 0.1 to 3 parts by weight in terms of SiO 2 based on 100 parts by weight of the conductive particles. A partially hydrolyzed condensate of tetraoxodecane."("Request Item 1"); silver particles as conductive fine particles ("Request Item 4").

又，在專利文獻2中記載有如下內容：“一種太陽能電池用導電性膏，其特徵為，含有黏結劑樹脂、溶劑、玻璃粉、以及將銀或銀化合物作為主要成分之導電性粉末，並且含有Si類有機化合物。”(「請求項1」)。 Further, Patent Document 2 discloses a conductive paste for a solar cell, which comprises a binder resin, a solvent, a glass frit, and a conductive powder containing silver or a silver compound as a main component, and Contains Si-based organic compounds." ("Request 1").

先行技術文獻 Advanced technical literature 專利文獻 Patent literature

專利文獻1：日本特開2008-135203號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-135203

專利文獻2：日本特開2010-87251號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-87251

但是，本發明者對專利文獻1及2所記載之膏材料進行研究的結果，清楚地發現，通過在200℃以下的低溫燒成來形成電極時，相對於矽基板或透明導電氧化膜(Transparent Conducting Oxide)(以下稱為「TCO」)之黏著性無法充分地發揮。 However, as a result of examining the paste materials described in Patent Documents 1 and 2, the present inventors have clearly found that when an electrode is formed by firing at a low temperature of 200 ° C or lower, the substrate is opposed to a tantalum substrate or a transparent conductive oxide film (Transparent). The adhesion of Conducting Oxide (hereinafter referred to as "TCO") cannot be fully exerted.

因此，本發明之課題在於提供一種能夠形成對於矽基板或TCO的黏著性優異電極之太陽能電池集電電極形成用導電性組成物與使用該組成物之太陽能電池單元。 Therefore, an object of the present invention is to provide a conductive composition for forming a solar cell current collector electrode which can form an electrode excellent in adhesion to a tantalum substrate or a TCO, and a solar battery cell using the same.

為了解決上述課題，本發明者經過戮力研究之結果，發現含有銀粉與特定之矽烷化合物的太陽能電池集電電極形成用導電性組成物對於矽基板或TCO之黏著性優異電極，因此完成本發明。亦即，本發明提供下述(1)~(13)： In order to solve the problem, the inventors of the present invention have found that the conductive composition for forming a solar cell current collecting electrode containing a silver powder and a specific decane compound has an excellent adhesion to a tantalum substrate or a TCO, and thus completed the present invention. . That is, the present invention provides the following (1) to (13):

(1)一種太陽能電池集電電極形成用導電性組成物，其特徵為含有銀粉(A)與下述式(I)表示之矽烷化合物(B)。 (1) A conductive composition for forming a collector electrode for a solar cell, which comprises a silver powder (A) and a decane compound (B) represented by the following formula (I).

(式中，R1及R2分別獨立表示烷基，R3表示可以具有雜原子之2價烷烴，m表示1~3之整數，複數之R1和R2分別可為相同也可為不同。)。 (wherein R 1 and R 2 each independently represent an alkyl group, R 3 represents a divalent alkane which may have a hetero atom, m represents an integer of 1 to 3, and plural R 1 and R 2 may be the same or different .).

(2)如上述(1)之太陽能電池集電電極形成用導電性組成物，其中，上述銀粉(A)之至少一部分為平均粒徑0.5~10μm之球狀銀粉末。 (2) The conductive composition for forming a current collector of a solar cell according to the above (1), wherein at least a part of the silver powder (A) is a spherical silver powder having an average particle diameter of 0.5 to 10 μm.

(3)如上述(1)或(2)之太陽能電池集電電極形成用導電性組成物，其中，矽烷化合物(B)在式(I)中，R1及R2分別獨立地表示甲基或乙基，R3表示碳數為2~10之伸烷基，m表示2或3。 (3) The conductive composition for forming a current collector electrode for a solar cell according to the above (1) or (2), wherein, in the formula (I), R 1 and R 2 each independently represent a methyl group. Or ethyl, R 3 represents an alkylene group having a carbon number of 2 to 10, and m represents 2 or 3.

(4)如上述(1)~(3)中任一項之太陽能電池集電電極形成用導電性組成物，其中，相對於100質量份之上述銀粉(A)，上述矽烷化合物(B)之含有量為0.05~1.0質量份。 (4) The conductive composition for forming a current collector electrode for a solar cell according to any one of the above (1), wherein the silane compound (B) is used for the silver powder (A) in an amount of 100 parts by mass. The content is 0.05 to 1.0 part by mass.

(5)如上述(1)~(4)中任一項之太陽能電池集電電極形成用導電性組成物，其中進而含有環氧樹脂(C)。 (5) The conductive composition for forming a current collector for a solar cell according to any one of the above (1) to (4), further comprising an epoxy resin (C).

(6)如上述(1)~(5)中任一項之太陽能電池集電電極形成用導電性組成物，其中進而含有脂肪酸銀鹽(D)。 (6) The conductive composition for forming a current collector for a solar cell according to any one of the above (1) to (5), further comprising a fatty acid silver salt (D).

(7)如上述(5)或(6)之太陽能電池集電電極形成用導電性組成物，其中上述之環氧樹脂(C)至少是環氧當量為1500~4000g/eq之雙酚A型環氧樹脂(C1)與環氧當量為1000g/eq以下之多元醇類縮水甘油醚型環氧樹脂(C2)。 (7) The conductive composition for forming a collector electrode for a solar cell according to the above (5) or (6), wherein the epoxy resin (C) is at least a bisphenol A type having an epoxy equivalent of 1500 to 4000 g/eq. The epoxy resin (C1) and the polyol glycidyl ether type epoxy resin (C2) having an epoxy equivalent of 1000 g/eq or less.

(8)如上述(6)或(7)之太陽能電池集電電極形成用導電性組成物，其中上述之脂肪酸銀鹽(D)為分別具有一個以上羧基銀鹽基(-COOAg)和羥基(-OH)的脂肪酸銀鹽(D1)和/或具有三個以上羧基銀鹽基(-COOAg)的聚羧酸銀鹽(D2)。 (8) The conductive composition for forming a collector electrode for a solar cell according to the above (6) or (7), wherein the above-mentioned fatty acid silver salt (D) has one or more carboxy silver salt groups (-COOAg) and a hydroxyl group ( -OH) fatty acid silver salt (D1) and/or polycarboxylate silver salt (D2) having three or more carboxyl silver salt groups (-COOAg).

(9)如上述(8)之太陽能電池集電電極形成用導電性組成物，其中上述之脂肪酸銀鹽(D1)為2,2-雙(羥基甲基)-正丁酸銀鹽和/或2-羥基異丁酸銀鹽。 (9) The conductive composition for forming a solar cell collector electrode according to the above (8), wherein the above-mentioned fatty acid silver salt (D1) is a 2,2-bis(hydroxymethyl)-n-butyric acid silver salt and/or Silver salt of 2-hydroxyisobutyrate.

(10)如上述(8)或(9)之太陽能電池集電電極形成用導電性組成物，其中上述之聚羧酸銀鹽(D2)為1,2,3,4-丁烷四羧酸銀鹽。 (10) The conductive composition for forming a collector electrode for a solar cell according to the above (8) or (9), wherein the above-mentioned polycarboxylate silver salt (D2) is 1,2,3,4-butanetetracarboxylic acid Silver salt.

(11)如上述(5)~(10)中任一項之太陽能電池集電電極形成用導電性組成物，其中相對於100質量份之上述銀粉(A)，上述環氧樹脂(C)之含有量為2~20質量份。 The conductive composition for forming a current collector electrode for a solar cell according to any one of the above aspects, wherein the epoxy resin (C) is used for 100 parts by mass of the silver powder (A). The content is 2 to 20 parts by mass.

(12)如上述(6)~(11)中任一項之太陽能電池集電電極形成用導電性組成物，其中相對於100質量份之上述銀粉(A)，上述脂肪酸銀鹽(D)之含有量為0.1~10質量份。 (12) The conductive composition for forming a collector electrode for a solar cell according to any one of the above (6), wherein the silver salt (D) of the above-mentioned silver powder (A) is used with respect to 100 parts by mass of the silver powder (A). The content is 0.1 to 10 parts by mass.

(13)一種太陽能電池單元，其特徵為，具有受光面一側之表面電極、半導體基板以及背面電極，且使用上述(1)~(12)中任一項之太陽能電池集電電極形成用導電性組成物形成上述表面電極和/或上述背面電極。 (13) A solar cell comprising a surface electrode on a light-receiving surface side, a semiconductor substrate, and a back surface electrode, and the solar cell collector electrode forming conductive layer according to any one of the above (1) to (12) The composition forms the above surface electrode and/or the above back electrode.

如下所示，根據本發明，能夠提供一種可形成對於矽基板或TCO之黏著性優異電極之太陽能電池集電電極形成用導電性組成物與使用該組成物之太陽能電池單元。 As described below, according to the present invention, it is possible to provide a conductive composition for forming a solar cell collecting electrode which can form an electrode excellent in adhesion to a ruthenium substrate or a TCO, and a solar battery cell using the same.

尤其，本發明之太陽能電池集電電極形成用導電性組成物，於異質結合太陽能電池之製造過程中，即使是通過200℃以下之低溫燒成也能形成與TCO之黏著性優異之電極，因此極為有用。 In particular, the conductive composition for forming a current collector for a solar cell of the present invention can form an electrode having excellent adhesion to TCO even when fired at a low temperature of 200 ° C or lower in the production process of a heterojunction solar cell. Extremely useful.

欲實施發明之型態 Type of invention to be implemented

本發明之太陽能電池集電電極形成用導電性組成物(下面簡稱為「本發明之導電性組成物」)，其中含有銀粉(A)與上述式(I)所表示之矽烷化合物(B)。 The conductive composition for forming a current collecting electrode for a solar cell of the present invention (hereinafter simply referred to as "the conductive composition of the present invention") contains silver powder (A) and a decane compound (B) represented by the above formula (I).

以下，關於銀粉(A)及矽烷化合物(B)以及根據所需所含有之其他成分等詳細地說明。 Hereinafter, the silver powder (A) and the decane compound (B), and other components contained as required, etc. are explained in detail.

<銀粉(A)> <Silver powder (A)>

在本發明之導電性組成物中所使用之銀粉(A)沒有特別限定，可以使用混合於過去周知之導電性膏中的銀粉。 The silver powder (A) used in the conductive composition of the present invention is not particularly limited, and silver powder mixed with a conventionally known conductive paste can be used.

由印刷性良好、可形成體積阻抗率小之電極等之理由考量，使用上述銀粉(A)作為其中至少一部分之平均粒徑0.5~10μm之球狀銀粉末為佳。 The silver powder (A) is preferably used as the spherical silver powder having an average particle diameter of 0.5 to 10 μm, at least a part of which is considered to be excellent in printability and an electrode having a small volume resistivity.

在此，所謂球狀是指，長徑與短徑比率為2以下之粒子的形狀。 Here, the spherical shape means a shape of particles having a ratio of long diameter to short diameter of 2 or less.

另外，所謂平均粒徑是指，球狀銀粉末之粒徑的平均值，且指利用雷射衍射式粒度分佈測量儀測量之50%體積累積粒徑(D50)。此外，作為計算平均值基礎之粒徑，在球狀銀粉末的截面為橢圓形時將該長徑與短徑的合計值 除以2的平均值，在球狀銀粉末的截面為正圓形時指該直徑。 In addition, the average particle diameter means the average value of the particle diameter of the spherical silver powder, and means the 50% volume cumulative particle diameter (D50) measured by the laser diffraction type particle size distribution measuring instrument. Further, as the particle diameter based on the calculation of the average value, when the cross section of the spherical silver powder is elliptical, the total value of the long diameter and the short diameter is Dividing by the average value of 2 means that the diameter of the spherical silver powder is a perfect circle.

另外，從印刷性較好的理由考量，上述銀粉(A)之平均粒徑0.7~5μm為佳，從燒成速度適當且作業性優異之理由考量，上述銀粉(A)之平均粒徑更佳為1~3μm。 In addition, the average particle diameter of the silver powder (A) is preferably 0.7 to 5 μm from the viewpoint of good printability, and the average particle diameter of the silver powder (A) is preferably considered from the viewpoint of appropriate firing rate and excellent workability. It is 1~3μm.

並且，上述銀粉(A)可以同時使用上述之球狀的銀粉末與薄片狀的銀粉末。 Further, the silver powder (A) may be used in combination with the spherical silver powder and the flake silver powder.

在此，同時使用薄片狀之銀粉末時，上述之球狀銀粉末之含有量為上述銀粉(A)總質量之中60質量%以上為佳。 When the flaky silver powder is used at the same time, the content of the spherical silver powder is preferably 60% by mass or more based on the total mass of the silver powder (A).

在本發明中，此般銀粉(A)可以使用市售品，作為其具體例，可舉出：AgC-102(形狀：球狀、平均粒徑：1.5μm、福田金屬箔粉工業社製造)、AgC-103(形狀：球狀、平均粒徑：1.5μm、福田金屬箔粉工業社製造)、AG4-8F(形狀：球狀、平均粒徑：2.2μm、同和電子社製造)、AG2-1C(形狀：球狀、平均粒徑：1.0μm、同和電子社製造)、AG3-11F(形狀：球狀、平均粒徑：1.4μm、同和電子社製造)、EHD(形狀：球狀、平均粒徑：0.5μm、三井金屬社製造)、AgC-2011(形狀：薄片狀、平均粒徑：2~10μm、福田金屬箔粉工業社製造)、AgC-301K(形狀：薄片狀、平均粒徑：3~10μm、福田金屬箔粉工業社製造)等。 In the present invention, a commercially available product can be used as the silver powder (A). Specific examples thereof include AgC-102 (shape: spherical shape, average particle diameter: 1.5 μm, manufactured by Fukuda Metal Foil Powder Co., Ltd.). , AgC-103 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Powder Co., Ltd.), AG4-8F (shape: spherical, average particle size: 2.2 μm, manufactured by Hosei Electronics Co., Ltd.), AG2- 1C (shape: spherical shape, average particle diameter: 1.0 μm, manufactured by Tonghe Electronics Co., Ltd.), AG3-11F (shape: spherical shape, average particle diameter: 1.4 μm, manufactured by Hosei Electronics Co., Ltd.), EHD (shape: spherical, average) Particle size: 0.5 μm, manufactured by Mitsui Metals Co., Ltd., AgC-2011 (shape: flake, average particle size: 2 to 10 μm, manufactured by Fukuda Metal Foil Co., Ltd.), AgC-301K (shape: flake, average particle diameter) : 3~10μm, manufactured by Foton Metal Foil Powder Co., Ltd.).

<矽烷化合物(B)> <decane compound (B)>

本發明之導電性組成物中所使用之矽烷化合物(B)是 由下述式(I)表示之化合物。 The decane compound (B) used in the conductive composition of the present invention is A compound represented by the following formula (I).

式中，R1及R2分別獨立表示烷基，R3表示可以具有雜原子之2價烷烴，m表示1~3之整數。複數之R1及R2分別可為相同也可為不同。 In the formula, R 1 and R 2 each independently represent an alkyl group, R 3 represents a divalent alkane which may have a hetero atom, and m represents an integer of 1 to 3. The plural R 1 and R 2 may be the same or different.

在此，上述式(I)中，作為R1和R2之烷基可舉例如碳數為1~6之烷基，具體而言，可以舉出甲基、乙基、n-丙基、n-丁基、n-戊基、n-己基。其中，較佳為甲基、乙基。 Here, in the above formula (I), examples of the alkyl group of R 1 and R 2 include an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. N-butyl, n-pentyl, n-hexyl. Among them, a methyl group or an ethyl group is preferred.

另外，上述式(I)中，作為R3之烷烴可舉例如可具有雜原子之碳數為2~10的烷基，具體而言，可以舉出乙烯基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基、癸烷-1,10-二基、N,N-二丙胺-3,3’-二基(-H6C3-NH-C3H6-)等。 In the above formula (I), examples of the alkane of R 3 include an alkyl group having a carbon number of 2 to 10 which may have a hetero atom, and specific examples thereof include a vinyl group and a propane-1,3-diyl group. Butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl , decane-1,9-diyl, decane-1,10-diyl, N,N-dipropylamine-3,3'-diyl (-H 6 C 3 -NH-C 3 H 6 -) Wait.

另外，上述式(I)中，m為2或3為佳。 Further, in the above formula (I), m is preferably 2 or 3.

作為在上述式(I)中表示之矽烷化合物(B)，具體而言，可以舉出如1,2-雙(三乙氧基甲矽烷基)乙烷、1,6-雙(三甲氧基甲矽烷基)己烷、1,7-雙(三甲氧基甲矽烷基)庚烷、1,8-雙(三甲氧基甲矽烷基)辛烷、1,9-雙(三甲氧基甲矽烷基)壬烷、1,10-雙(三甲氧基甲矽烷基)癸烷等雙(三烷氧基 甲矽烷基)烷烴；N,N-雙[(3-三甲氧基甲矽烷基)丙基]胺、N,N-雙[(3-三乙氧基甲矽烷基)丙基]胺、N,N-雙[(3-三丙氧基甲矽烷基)丙基]胺等雙(氧烷基甲矽烷基烷基)胺等。 Specific examples of the decane compound (B) represented by the above formula (I) include 1,2-bis(triethoxycarbenyl)ethane and 1,6-bis(trimethoxy). Carbenyl)hexane, 1,7-bis(trimethoxymethylidene) heptane, 1,8-bis(trimethoxymethylidene)octane, 1,9-bis(trimethoxymethane Bis(trial alkoxy) such as decane or 1,10-bis(trimethoxymethyl decyl) decane Methanealkyl)alkane; N,N-bis[(3-trimethoxycarbamidino)propyl]amine, N,N-bis[(3-triethoxymethyl)alkyl]amine, N A bis(oxyalkylcarbaminyalkyl)amine such as N-bis[(3-tripropoxymethyl)alkyl]amine.

其中，1,2-雙(三乙氧基甲矽烷基)乙烷、1,6-雙(三甲氧基甲矽烷基)己烷、N,N-雙[(3-三甲氧基甲矽烷基)丙基]胺為佳。 Among them, 1,2-bis(triethoxycarbenyl)ethane, 1,6-bis(trimethoxyformamido)hexane, N,N-bis[(3-trimethoxycarbendyrylene) Acrylamine is preferred.

本發明之導電性組成物由於包括上述矽烷化合物(B)，因此能夠形成對於矽基板或TCO之黏著性優異的電極。 Since the conductive composition of the present invention includes the above-described decane compound (B), it is possible to form an electrode excellent in adhesion to a ruthenium substrate or TCO.

雖然詳細原因不明確，但認為是因為如下的原因，即考量到在後述之比較例中所使用的己基三甲氧基矽烷中黏著性之改善效果不明顯，通過上述矽烷化合物(B)具有兩個烷氧基甲矽烷基，由此所形成之電極與矽基板或TCO之間形成交聯。 Although the detailed reason is not clear, it is considered to be because the effect of improving the adhesion in hexyltrimethoxydecane used in the comparative example described later is not significant, and the decane compound (B) has two The alkoxycarbenyl group, whereby the electrode formed forms a crosslink with the tantalum substrate or TCO.

在本發明中，從對於所形成之電極的體積阻抗率和對於矽基板或TCO之黏著性和均衡性優異之理由考量，相對於100質量份之上述銀粉(A)，上述矽烷化合物(B)之含有量0.05~1.0質量份為佳，較佳為0.1~0.7質量份。 In the present invention, the above-described decane compound (B) is considered with respect to 100 parts by mass of the above silver powder (A) from the viewpoint of the volume resistivity of the formed electrode and the adhesion and balance to the tantalum substrate or TCO. The content is preferably 0.05 to 1.0 part by mass, preferably 0.1 to 0.7 part by mass.

<環氧樹脂(C)> <Epoxy Resin (C)>

本發明的導電性組成物進而較適合為根據需要作為造模性樹脂進而包含環氧樹脂(C)。 The conductive composition of the present invention is further suitably used as a mold-forming resin and further contains an epoxy resin (C) as needed.

作為上述環氧樹脂(C)可以使用現有周知的環氧樹脂。 As the epoxy resin (C), a conventionally known epoxy resin can be used.

具體而言，可以舉出如雙酚A型、雙酚F型、溴化雙酚A型、氫化雙酚A型、雙酚S型、雙酚AF型等雙酚型環氧樹脂；乙二醇縮水甘油醚、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、新戊二醇二縮水甘油醚、聚新戊二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、聚丙三醇聚縮水甘油醚、聚氧基乙二醇二縮水甘油醚、二丙三醇聚縮水甘油醚、聚丙三醇聚縮水甘油醚、山梨糖醇聚縮水甘油醚、聚四甲二醇二縮水甘油醚、季戊四醇二縮水甘油醚、季戊四醇三縮水甘油醚、聚季戊四醇聚縮水甘油醚、三甲基丙烷二縮水甘油醚、四(縮水甘油醚氧基苯基)乙烷、三(縮水甘油醚氧基)甲烷等多元醇類縮水甘油醚型環氧樹脂；二聚酸等合成脂肪酸的縮水甘油酯類環氧樹脂；N,N,N',N'-四縮水甘油基二氨基二苯甲烷(TGDDM)、四縮水甘油基二氨基二苯碸(TGDDS)、四縮水甘油基間二甲苯二胺(TGMXDA)、三縮水甘油基對氨基苯酚、三水甘油基-間氨基苯酚、N,N-二縮水甘油基苯胺、四縮水甘油基1,3-雙氨基甲基環己烷(TG1,3-BAC)、三縮水甘油基異氰酸酯(TGIC)等縮水甘油基胺類環氧樹脂；這些可以單獨使用一種，也可以同時使用兩種以上。 Specific examples thereof include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, and bisphenol AF type; Glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl Alcohol diglycidyl ether, polyneopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , polypropylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, polyoxyethylene glycol diglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polycondensate Glycerol ether, sorbitol polyglycidyl ether, polytetramethylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, polypentaerythritol polyglycidyl ether, trimethylpropane diglycidyl ether, four (glycidyloxyphenyl) ethane, three (shrinkage) Polyol glycidyl ether epoxy resin such as oleyloxy)methane; glycidyl ester epoxy resin of synthetic fatty acid such as dimer acid; N,N,N',N'-tetraglycidyldiamino Benzene methane (TGDDM), tetraglycidyldiaminodiphenyl hydrazine (TGDDS), tetraglycidyl metaxylenediamine (TGMXDA), triglycidyl p-aminophenol, triglycidyl-m-aminophenol, N a glycidylamine epoxy resin such as N-diglycidylaniline, tetraglycidyl1,3-1,3-aminomethylcyclohexane (TG1,3-BAC) or triglycidyl isocyanate (TGIC); These may be used alone or in combination of two or more.

本發明中，從能夠形成焊接性良好的電極的理由考量，上述環氧樹脂(C)同時使用環氧當量為1500~4000g/eq的雙酚A型環氧樹脂(C1)和環氧當量為1000g/eq以下的多元醇類縮水甘油醚型環氧樹脂(C2)為佳。 In the present invention, in consideration of the reason that an electrode having good weldability can be formed, the epoxy resin (C) is simultaneously used as a bisphenol A type epoxy resin (C1) having an epoxy equivalent of 1500 to 4000 g/eq and an epoxy equivalent. A polyol glycidyl ether type epoxy resin (C2) of 1000 g/eq or less is preferred.

(雙酚A型環氧樹脂(C1)) (bisphenol A type epoxy resin (C1))

上述雙酚A型環氧樹脂(C1)是環氧當量為1500~4000g/eq的雙酚A型環氧樹脂。 The bisphenol A type epoxy resin (C1) is a bisphenol A type epoxy resin having an epoxy equivalent of 1500 to 4000 g/eq.

上述雙酚A型環氧樹脂(C1)的環氧當量為上述範圍時，本發明的導電性組成物的固化後的硬度變為良好，能夠維持相對於固化物(電極)的良好的焊接性。 When the epoxy equivalent of the bisphenol A type epoxy resin (C1) is in the above range, the hardness of the conductive composition of the present invention after curing is good, and it is possible to maintain good weldability with respect to the cured product (electrode). .

另外，從相對於電極的焊接性更良好、降低固化收縮比例且抑制太陽能電池單元基板的翹曲的理由考量，上述雙酚A型環氧樹脂(C1)的環氧當量2000~4000g/eq為佳，更佳為2000~3500g/eq。 Further, considering the reason that the weldability with respect to the electrode is better, the ratio of curing shrinkage is lowered, and the warpage of the solar cell substrate is suppressed, the epoxy equivalent of the bisphenol A type epoxy resin (C1) is 2,000 to 4,000 g/eq. Better, better than 2000~3500g/eq.

(多元醇類縮水甘油醚型環氧樹脂(C2)) (Polyol type glycidyl ether type epoxy resin (C2))

上述多元醇類縮水甘油醚型環氧樹脂(C2)是環氧當量為1000g/eq以下的多元醇類縮水甘油醚型環氧樹脂。 The polyol glycidyl ether type epoxy resin (C2) is a polyol glycidyl ether type epoxy resin having an epoxy equivalent of 1000 g/eq or less.

上述多元醇類縮水甘油醚型環氧樹脂(C2)的環氧當量為上述範圍時，本發明的導電性組成物的黏度變為良好，且印刷性變為良好。 When the epoxy equivalent of the polyol-glycidyl ether type epoxy resin (C2) is in the above range, the viscosity of the conductive composition of the present invention becomes good, and the printability becomes good.

另外，從進行絲網印刷時的黏度變為適當的理由考量，上述多元醇類縮水甘油醚型環氧樹脂(C2)的環氧當量 100~400g/eq為佳，更佳為100~300g/eq。 In addition, the epoxy equivalent of the above-described polyol glycidyl ether type epoxy resin (C2) is considered from the viewpoint of the viscosity at the time of screen printing becoming appropriate. 100 to 400 g/eq is preferred, and more preferably 100 to 300 g/eq.

另外，從能夠形成矽基板或TCO的黏著性更良好的電極的理由考量，上述環氧樹脂(C)以加成環氧乙烷和/或環氧丙烷的環氧樹脂(C3)為佳。 Further, the epoxy resin (C) is preferably an epoxy resin (C3) to which ethylene oxide and/or propylene oxide is added, from the viewpoint of forming an electrode having a better adhesion to a tantalum substrate or a TCO.

在此，環氧乙烷和/或環氧丙烷的加成，例如使雙酚A、雙酚F等與表氯醇反應而製造環氧樹脂時，通過添加乙烯和/或丙烯能夠加成(改性)。 Here, the addition of ethylene oxide and/or propylene oxide, for example, when bisphenol A, bisphenol F, etc. are reacted with epichlorohydrin to produce an epoxy resin, can be added by adding ethylene and/or propylene ( modified).

作為上述環氧樹脂(C3)可以使用市售品，作為其具體例子，可以舉出如環氧乙烷加成雙酚A型環氧樹脂(BEO-60E，新日本理化社製造)、環氧丙烷加成雙酚A型環氧樹脂(BPO-20E，新日本理化社製造)、環氧丙烷加成雙酚A型環氧樹脂(EP-4010S，ADEKA社製造)、環氧丙烷加成雙酚A型環氧樹脂(EP-4000S，ADEKA社製造)等。 A commercially available product can be used as the epoxy resin (C3), and specific examples thereof include ethylene oxide addition bisphenol A type epoxy resin (BEO-60E, manufactured by Nippon Chemical and Chemical Co., Ltd.), and epoxy resin. Propane addition bisphenol A type epoxy resin (BPO-20E, manufactured by Nippon Chemical and Chemical Co., Ltd.), propylene oxide addition bisphenol A type epoxy resin (EP-4010S, manufactured by ADEKA), propylene oxide addition double A phenol A type epoxy resin (EP-4000S, manufactured by ADEKA Co., Ltd.) or the like.

進而，本發明中，從能夠形成相對於矽基板或TCO的黏著性更良好的電極的理由考量，相對於100質量份的上述銀粉(A)，包括上述環氧樹脂(C)時的含有量2~20質量份為佳，更佳為2~10質量份，特佳為3.5~7質量份。 Furthermore, in the present invention, the content of the above-mentioned epoxy resin (C) is included with respect to 100 parts by mass of the silver powder (A), from the viewpoint of being able to form an electrode having a better adhesion to the tantalum substrate or the TCO. 2 to 20 parts by mass is more preferably 2 to 10 parts by mass, and particularly preferably 3.5 to 7 parts by mass.

<脂肪酸銀鹽(D)> <Fatty acid silver salt (D)>

從即使是200℃以下的低溫下的燒成也可形成體積阻抗率低的電極的理由考量，本發明的導電性組成物進而含有脂肪酸銀鹽(D)為佳。 The reason why the electrode having a low volume resistivity can be formed by firing at a low temperature of 200 ° C or lower is preferable, and the conductive composition of the present invention further contains a fatty acid silver salt (D).

上述脂肪酸銀鹽(D)只要是有機羧酸的銀鹽就無特別限定，例如可使用日本特開2008-198595號公報的 [0063]~[0068]段所記載之脂肪酸金屬鹽(特別是三級脂肪酸銀鹽)、特許第4482930號公報的[0030]段所記載之脂肪酸銀、特開2010-92684號公報的[0029]~[0045]段所記載之具有一個以上羥基的脂肪酸銀鹽、同一公報的[0046]~[0056]段所記載之二級脂肪酸銀鹽等。 The above-mentioned fatty acid silver salt (D) is not particularly limited as long as it is a silver salt of an organic carboxylic acid, and for example, JP-A-2008-198595 can be used. [0063] The fatty acid metal salt (particularly the tertiary fatty acid silver salt) described in the paragraph [0068], the fatty acid silver described in paragraph [0030] of Japanese Patent No. 4482930, and the [0029] of JP-A-2010-92684 The fatty acid silver salt having one or more hydroxyl groups described in the paragraph [0045], the secondary fatty acid silver salt described in paragraphs [0046] to [0056] of the same publication, and the like.

在這些鹽中，從即使是在更低溫(150℃~180℃程度)下的燒成也能夠形成體積阻抗率低的電極的理由考量，使用分別具有一個以上羧基銀鹽基(-COOAg)和羥基(-OH)的脂肪酸銀鹽(D1)和/或具有三個以上羧基銀鹽基(-COOAg)的聚羧酸銀鹽(D2)為佳。 Among these salts, it is possible to form an electrode having a low volume resistivity even when it is fired at a lower temperature (about 150 ° C to 180 ° C), and one or more carboxyl group-containing silver groups (-COOAg) are used. A fatty acid silver salt (D1) of a hydroxyl group (-OH) and/or a polycarboxylic acid silver salt (D2) having three or more carboxyl silver salt groups (-COOAg) is preferred.

具體而言，例如，作為上述脂肪酸銀鹽(D1)，使用2,2-雙(羥基甲基)-正丁酸銀鹽、2-羥基異丁酸銀鹽，作為上述聚羧酸銀鹽(D2)，可優選使用1,2,3,4-丁烷四羧酸銀鹽為佳。 Specifically, for example, as the above-mentioned fatty acid silver salt (D1), a silver salt of 2,2-bis(hydroxymethyl)-n-butyrate or a silver salt of 2-hydroxyisobutyric acid is used as the above-mentioned silver salt of a polycarboxylic acid ( D2), a silver salt of 1,2,3,4-butanetetracarboxylate is preferably used.

在本發明中，從印刷性良好的理由考量，相對於100質量份的上述銀粉(A)，上述脂肪酸銀鹽(D)的含有量0.1~10質量份為佳，更佳為1~10質量份。 In the present invention, the content of the fatty acid silver salt (D) is preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the silver powder (A). Share.

<陽離子類固化劑(E)> <cationic curing agent (E)>

本發明的導電性組成物根據需要包括上述環氧樹脂(C)時，作為環氧樹脂的固化劑含有陽離子類固化劑(E)為佳。 When the conductive composition of the present invention includes the above epoxy resin (C) as needed, it is preferred to contain a cationic curing agent (E) as a curing agent for the epoxy resin.

上述陽離子類固化劑(E)並無特別限定，胺類、鋶類、銨類、磷類的固化劑為佳。 The cationic curing agent (E) is not particularly limited, and an amine, an anthracene, an ammonium or a phosphorus curing agent is preferred.

作為上述陽離子類固化劑(E)，具體而言，可以舉出如三氟化硼乙胺、三氟化硼呱啶、三氟化硼苯酚、p-甲氧基苯重氮六氟磷酸、二苯鍰六氟磷酸、四苯基鋶、四-n-丁基磷四苯基硼酸、四-n-丁基磷-o、o-二甲基二硫代磷酸酯、由下述式(I)表示的鋶鹽等，這些可以單獨使用一種，也可以同時使用兩種以上。 Specific examples of the cationic curing agent (E) include boron trifluoride bromide, boron trifluoride aboride, boron trifluoride phenol, and p-methoxybenzenediazonium hexafluorophosphate. Diphenylphosphonium hexafluorophosphate, tetraphenylphosphonium, tetra-n-butylphosphonium tetraphenylboronic acid, tetra-n-butylphosphorus-o, o-dimethyldithiophosphate, by the following formula ( I) may be used singly or in combination of two or more kinds.

其中，從固化時間變短之理由考量，由下述式(Ⅱ)表示之鋶鹽為佳。 Among them, the onium salt represented by the following formula (II) is preferable in view of the reason why the curing time is shortened.

(式中，R4表示氫原子、碳數為1~4的烷基或鹵原子，R5表示碳數為1~4的烷基、也可以由碳數為1~4的烷基取代的苄基或α-萘基甲基，R6表示碳數為1~4的烷基。另外，Q為由下述式(a)~(c)的任一項表示的基，X表示SbF6、PF6、CF3SO3、(CF3SO2)2N、BF4、B(C6F5)4或Al(CF3SO3)4)。 (wherein R 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 5 represents an alkyl group having 1 to 4 carbon atoms, or may be substituted by an alkyl group having 1 to 4 carbon atoms; Benzyl or α-naphthylmethyl, and R 6 represents an alkyl group having 1 to 4 carbon atoms. Further, Q is a group represented by any one of the following formulas (a) to (c), and X represents SbF 6 . PF 6 , CF 3 SO 3 , (CF 3 SO 2 ) 2 N, BF 4 , B(C 6 F 5 ) 4 or Al(CF 3 SO 3 ) 4 ).

(式(a)中，R表示氫原子、乙醯基、甲氧基羰基或苄基氧基羰基。) (In the formula (a), R represents a hydrogen atom, an ethenyl group, a methoxycarbonyl group or a benzyloxycarbonyl group.)

由上述式(Ⅱ)表示之鋶鹽中，從可形成焊接性更優異之電極的理由考量，上述式(Ⅱ)中，X由SbF6所表示之鋶鹽為佳，作為此具體例，可舉出由下述式(1)和(2)所表示之化合物。 In the sulfonium salt represented by the above formula (II), from the viewpoint of forming an electrode having more excellent weldability, in the above formula (II), X is preferably a sulfonium salt represented by SbF 6 , and as a specific example, The compounds represented by the following formulas (1) and (2) are mentioned.

又，本發明中，從通過熱活性化而能夠使環氧基的開環反應充分進行之理由考量，相對於上述100質量份之環氧樹脂(C)，上述陽離子類固化劑(E)之含有量1~10質量 份為佳，1~5質量份更佳。 In the present invention, the cationic curing agent (E) is used for the epoxy resin (C) in an amount of 100 parts by mass based on the reason that the ring-opening reaction of the epoxy group can be sufficiently carried out by thermal activation. Content 1~10 mass The serving is better, preferably 1 to 5 parts by mass.

<溶劑(F)> <Solvent (F)>

從印刷性等作業性的觀點考量，本發明之導電性組成物進一步含有溶劑(F)為佳。 It is preferable that the conductive composition of the present invention further contains a solvent (F) from the viewpoint of workability such as printability.

上述溶劑(F)只要是能夠將本發明之導電性組成物塗覆於基材上之溶劑並無特別限定，作為其具體例，可舉例如丁基卡必醇、甲基乙基酮、異佛爾酮、α-萜品醇等，這些可以單獨使用一種，也可以同時使用兩種以上。 The solvent (F) is not particularly limited as long as it can apply the conductive composition of the present invention to a substrate, and specific examples thereof include butyl carbitol, methyl ethyl ketone, and the like. For example, phorone, α -terpineol, or the like may be used alone or in combination of two or more.

另外，在含有上述溶劑(F)時之含有量，相對於100質量份之上述銀粉(A)，2~20質量份為佳，5~15質量份更佳。 In addition, the content of the solvent (F) is preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass, per 100 parts by mass of the silver powder (A).

<添加劑> <additive>

依據需要，本發明之導電性組成物可以含有除上述銀粉(A)以外之金屬粉、還原劑等添加劑。 The conductive composition of the present invention may contain an additive such as a metal powder or a reducing agent other than the silver powder (A) as needed.

作為上述金屬粉，具體而言，可舉出如銅、鋁等，其中銅為佳。另外，0.01~10μm粒徑之金屬粉為佳。 Specific examples of the metal powder include copper, aluminum, and the like, and copper is preferred. Further, a metal powder having a particle diameter of 0.01 to 10 μm is preferred.

作為上述還原劑，具體而言，可舉出如乙二醇等。 Specific examples of the reducing agent include ethylene glycol and the like.

另一方面，從更加提高縱橫比、且抑制上述環氧樹脂(C)之分解的理由考量，相對於100質量份的上述溶劑(F)，氧化銀的含有量5質量份以下為佳，1質量份以下較佳，更佳為實質上不含有氧化銀。 On the other hand, from the viewpoint of further increasing the aspect ratio and suppressing the decomposition of the epoxy resin (C), the content of the silver oxide is preferably 5 parts by mass or less based on 100 parts by mass of the solvent (F). It is preferably 5% by mass or less, more preferably substantially free of silver oxide.

本發明之導電性組成物的製造方法沒有特別的限定， 可以舉出將上述銀粉(A)、上述矽烷化合物(B)和根據需要可含有上述環氧樹脂(C)以及上述脂肪酸銀鹽(D)、上述陽離子類固化劑(E)、上述溶劑(F)以及添加劑通過輥壓機、捏合機、擠壓機、萬能攪拌機等進行混合的方法。 The method for producing the conductive composition of the present invention is not particularly limited. The silver powder (A), the decane compound (B), and, if necessary, the epoxy resin (C) and the fatty acid silver salt (D), the cationic curing agent (E), and the solvent (F) may be contained. And a method in which the additive is mixed by a roll press, a kneader, an extruder, a universal mixer, or the like.

[太陽能電池單元] [Solar battery unit]

本發明之太陽能電池單元是具有受光面一側之表面電極、半導體基板以及背面電極、且使用上述本發明之導電性組成物形成上述表面電極和/或上述背面電極的太陽能電池單元。 The solar battery cell of the present invention is a solar battery cell having a surface electrode on the light-receiving surface side, a semiconductor substrate, and a back surface electrode, and the surface electrode and/or the back surface electrode are formed using the conductive composition of the present invention.

在此，由於本發明的太陽能電池單元的上述本發明的導電性組成物可適用於全背面電極型(所謂背接觸式)太陽能電池的背面電極的形成，所以可適用於全背面電極型太陽能電池。 Here, since the above-described conductive composition of the present invention of the solar battery cell of the present invention can be applied to the formation of the back surface electrode of a full back electrode type (so-called back contact type) solar cell, it can be applied to a full back electrode type solar cell. .

下面，利用圖1說明本發明之太陽能電池單元較佳之實施方式的一個例子。另外，在圖1中以薄膜類的非晶矽太陽能電池為例子對本發明的太陽能電池單元進行說明，但並不局限於此，例如，也可以是混合型(HIT)太陽能電池等。 Next, an example of a preferred embodiment of the solar battery cell of the present invention will be described with reference to Fig. 1 . Further, although the solar cell of the present invention is described as an example of a thin film-type amorphous germanium solar cell in FIG. 1, the present invention is not limited thereto, and for example, a hybrid (HIT) solar cell or the like may be used.

圖1為表示太陽能電池單元較佳之實施方式的一個例子的截面圖。 Fig. 1 is a cross-sectional view showing an example of a preferred embodiment of a solar battery cell.

太陽能電池單元1在塑膠薄膜基板9上含有：作為集電極的表面電極2、透明導電氧化膜(TCO)3、p型非晶矽層4、i型非晶矽層5和n型非晶矽層6所層壓的矽基板7 、作為金屬電極的背面電極8。 The solar battery cell 1 includes a surface electrode 2 as a collector electrode, a transparent conductive oxide film (TCO) 3, a p-type amorphous germanium layer 4, an i-type amorphous germanium layer 5, and an n-type amorphous germanium on the plastic film substrate 9.矽 substrate 7 laminated on layer 6 As the back electrode 8 of the metal electrode.

另外，太陽能電池單元1較佳是在其表面和背面上包括保護薄膜10。 Further, the solar battery cell 1 preferably includes a protective film 10 on its front and back surfaces.

構成矽基板7的非晶矽由於其原子排列不規則，因此與晶矽相比光和格子的相互作用變大，從而能夠吸收更多的光。因此，能夠使太陽能電池1薄膜化，能夠以1μm以下的薄膜發電。 Since the amorphous iridium constituting the ruthenium substrate 7 is irregular in atomic arrangement, the interaction between light and lattice is larger than that of the wafer, and more light can be absorbed. Therefore, the solar cell 1 can be made thinner, and it is possible to generate electricity from a thin film of 1 μm or less.

透明導電氧化膜3是通過在作為絕緣體的玻璃表面上形成錫摻雜氧化銦(ITO)、氧化錫(TO)、氟摻雜氧化錫(FTO)等半導體陶瓷的薄層來賦予導電性，因此即使是透明但具有導電性質。 The transparent conductive oxide film 3 is formed by forming a thin layer of a semiconductor ceramic such as tin-doped indium oxide (ITO), tin oxide (TO), or fluorine-doped tin oxide (FTO) on the surface of the glass as an insulator, thereby imparting conductivity. Even transparent but conductive.

<表面電極/背面電極> <surface electrode / back electrode>

本發明的太陽能電池單元具有的表面電極和背面電極只要是其中之一或兩者是使用本發明的導電性組成物而形成的，就對電極的配置(節距)、形狀、高度、寬度等並無特別限定。 The surface electrode and the back surface electrode of the solar cell of the present invention are formed by using one or both of the conductive compositions of the present invention, and the arrangement (pitch), shape, height, width, and the like of the counter electrode. There is no particular limitation.

在此，表面電極和背面電極通常具有多個，在本發明中，例如可以是多個表面電極中的僅有部分表面電極使用本發明的導電性組成物而形成，也可以是多個表面電極中的部分表面電極和多個背面電極中的部分背面電極使用本發明的導電性組成物而形成。 Here, the surface electrode and the back surface electrode are usually plural. In the present invention, for example, only a part of the surface electrodes of the plurality of surface electrodes may be formed using the conductive composition of the present invention, or may be a plurality of surface electrodes. A part of the surface electrode and a part of the back surface electrodes of the plurality of back electrodes are formed using the conductive composition of the present invention.

本發明的太陽能電池單元的製造方法沒有特別的限定，可舉出包括將本發明的導電性組成物塗覆在矽基板和/ 或TCO上以形成配線的配線形成步驟，以及對所得到的配線進行熱處理以形成電極(表面電極和/或背面電極)的熱處理步驟的方法。 The method for producing the solar battery cell of the present invention is not particularly limited, and includes coating the conductive composition of the present invention on a ruthenium substrate and/or Or a method of forming a wiring on the TCO, and a method of heat-treating the obtained wiring to form a heat treatment step of the electrode (surface electrode and/or back electrode).

以下，對配線形成步驟和熱處理步驟進行詳細說明。 Hereinafter, the wiring forming step and the heat treatment step will be described in detail.

<配線形成步驟> <Wiring forming step>

配線形成步驟是將本發明的導電性組成物塗覆在矽基板和/或TCO上以形成配線的步驟。 The wiring forming step is a step of coating the conductive composition of the present invention on a tantalum substrate and/or a TCO to form wiring.

在此，作為塗覆方法，具體可舉出例如，噴墨印刷、絲網印刷、凹版印刷、平版印刷、凸版印刷等。 Here, specific examples of the coating method include inkjet printing, screen printing, gravure printing, lithography, and letterpress printing.

<熱處理步驟> <heat treatment step>

熱處理步驟是對在上述配線形成步驟中所得到的塗膜進行熱處理以獲得導電性的配線(電極)的步驟。 The heat treatment step is a step of heat-treating the coating film obtained in the above-described wiring forming step to obtain conductive wiring (electrode).

在此，上述熱處理沒有特別的限定，但由於使用本發明的導電性組成物，因此即使在低溫(150~500℃以下)下也能夠實施良好的熱處理(燒成)。 Here, the heat treatment is not particularly limited. However, since the conductive composition of the present invention is used, good heat treatment (baking) can be performed even at a low temperature (150 to 500 ° C or lower).

另外，在上述配線形成步驟中所獲得的配線由於在紫外線或紅外線照射下也能夠形成電極，因此本發明中的熱處理步驟也可以是通過紫外線或紅外線照射的處理。 Further, since the wiring obtained in the wiring forming step described above can form an electrode even under irradiation of ultraviolet rays or infrared rays, the heat treatment step in the present invention may be a treatment by ultraviolet rays or infrared rays.

[實施例] [Examples]

以下，利用實施例對本發明的導電性組成物進行詳細 說明。但是，本發明並不限於此。 Hereinafter, the conductive composition of the present invention will be described in detail by way of examples. Description. However, the invention is not limited thereto.

(實施例1~9、比較例1~3) (Examples 1 to 9 and Comparative Examples 1 to 3)

在球磨機中添加下述第1表所示的銀粉等，以成為下述第1表所示的組合比，並對這些進行混合，由此製造導電性組成物。 The silver powder or the like shown in the first table below is added to the ball mill to form a combination ratio as shown in the first table below, and these are mixed to produce a conductive composition.

利用絲網印刷將所製造的導電性組成物塗覆在浸漬在鹼性蝕刻液中而去除表面氧化膜的矽基板(單晶矽片、LS-25TVA、156mm×156mm×200μm、信越化學工業社製造)上以形成作為25mm×25mm的固體塗層的測試圖案。 The produced conductive composition was coated on a tantalum substrate immersed in an alkaline etching solution to remove the surface oxide film by screen printing (single crystal wafer, LS-25 TVA, 156 mm × 156 mm × 200 μm, Shin-Etsu Chemical Co., Ltd. Manufactured to form a test pattern as a solid coating of 25 mm x 25 mm.

另外，同樣地，利用絲網印刷將所製造的導電性組成物塗覆在作為TCO的ITO沉積玻璃基板上以形成作為25mm×25mm的固體塗層的測試圖案。 Further, similarly, the produced conductive composition was coated on an ITO-deposited glass substrate as a TCO by screen printing to form a test pattern as a solid coating of 25 mm × 25 mm.

<體積阻抗率(比電阻)> <Volume impedance ratio (specific resistance)>

將形成有測試圖案的矽基板在100℃的條件下進行2分鐘的乾燥後在200℃的條件下燒成30分鐘，由此製造用於體積阻抗率測量的測試片。 The tantalum substrate on which the test pattern was formed was dried at 100 ° C for 2 minutes and then baked at 200 ° C for 30 minutes, thereby producing a test piece for volume resistivity measurement.

對於所製造的體積阻抗率測定用之測試片，通過使用阻抗率計(LORESTA-GP、三菱化學社製造)的四端子四探針法對電極的體積阻抗率進行了測量。這些結果表示在下述第1表。 The volume resistivity of the electrode was measured by a four-terminal four-probe method using an impedance meter (LORESTA-GP, manufactured by Mitsubishi Chemical Corporation) for the test piece for measuring the volume resistivity. These results are shown in the first table below.

另外，關於採用同樣的方法從形成有測試圖案的ITO沉積玻璃基板製造測試片，當採用同樣的方法測量體積阻 抗率時，其結果與下述第1表中所示的結果相同。 In addition, regarding the same method, a test piece was produced from an ITO-deposited glass substrate on which a test pattern was formed, and the volume resistance was measured in the same manner. When the resistance is high, the results are the same as those shown in Table 1 below.

<黏著性：矽基板> <Adhesiveness: 矽 Substrate>

採用與用於測量體積阻抗率的測試片相同的方法乾燥和燒成形成有測試圖案的矽基板，由此製造測試片。 The test piece was produced by drying and firing the tantalum substrate on which the test pattern was formed in the same manner as the test piece for measuring the volume resistivity.

接著，如圖2所示，將使用環氧類黏結劑(愛牢達(Araldite)AR-R30、亨斯邁(Huntsman)公司製造)11製造的測試片12(標號13：測試圖案、標號14：矽基板)固定在兩個不銹鋼板(長度：100mm、寬度25mm、厚度：1.5mm)15之間，由此製造用於評價黏著性的測試片。另外，通過環氧類黏結劑11的不銹鋼板15和測試圖案13之間的黏結面積為312.5mm2。 Next, as shown in FIG. 2, a test piece 12 manufactured using an epoxy-based adhesive (Araldite AR-R30, manufactured by Huntsman) 11 (reference numeral 13: test pattern, reference numeral 14) The crucible substrate was fixed between two stainless steel plates (length: 100 mm, width 25 mm, thickness: 1.5 mm) 15, thereby producing a test piece for evaluating adhesion. Further, the bonding area between the stainless steel plate 15 and the test pattern 13 passing through the epoxy-based adhesive 11 was 312.5 mm 2 .

將所製造的黏著性評價用測試片安裝在剪切剝離試驗機(RTC-1310A、ORIENTEC社製造(海計測特機株式會社))上，對一側的不銹鋼板向箭頭方向施加力，由此測量剪切剝離強度，並以目視來觀察剝離面。將其結果表示在下述第1表中。另外，在下述第1表中，“Si/SUS”表示矽基板和不銹鋼板的剝離，“Si/Ag”表示矽基板和測試圖案的剝離。 The test piece for adhesion evaluation was attached to a shear peeling tester (RTC-1310A, manufactured by ORIENTEC Co., Ltd.), and a force was applied to one side of the stainless steel plate in the direction of the arrow. The shear peel strength was measured, and the peeled surface was visually observed. The results are shown in the first table below. Further, in the first table below, "Si/SUS" indicates peeling of the tantalum substrate and the stainless steel sheet, and "Si/Ag" indicates peeling of the tantalum substrate and the test pattern.

<黏著性：ITO沉積玻璃> <Adhesiveness: ITO deposited glass>

同體積阻抗率測量用測試片一樣，將形成有測試圖案的ITO沉積玻璃進行乾燥和燒成，由此製造測試片。 The ITO deposited glass on which the test pattern was formed was dried and fired in the same manner as the test piece for measuring the volume resistivity, thereby producing a test piece.

接著，在所製造的測試片的測試圖案上以1mm節距 開有切縫，由此製造100個棋盤狀格子(10×10)，在整個棋盤狀格子上附著玻璃紙黏著膠帶，並用手指頭纏繞10圈後，將膠帶的一端以呈垂直的狀態瞬間拉開，然後調查沒有完全剝離而殘留的棋盤狀格子的數量。將其結果表示在下述第1表裏。 Next, a 1 mm pitch is applied to the test pattern of the manufactured test piece. A slit is formed, thereby manufacturing 100 checkerboard lattices (10×10), and a cellophane adhesive tape is attached to the entire checkerboard lattice, and after being wound with a finger for 10 turns, one end of the tape is pulled apart in a vertical state. Then, investigate the number of checkerboard lattices that remain without being completely stripped. The results are shown in the first table below.

另外，相對於全部100個棋盤狀格子(下述第1表中的分母)，如果殘留的棋盤狀格子的數量(下述第1表中的分子)為80個以上，則能夠評價相對於TCO的黏著性優異。 In addition, with respect to all the 100 checkerboard grids (the denominator in the first table below), if the number of the checkerboard grids remaining (the molecules in the first table below) is 80 or more, it is possible to evaluate the relative TCO. Excellent adhesion.

<焊接性(焊料潤濕性)> <welding property (solder wettability)>

在形成有測試圖案的矽基板和ITO沉積玻璃基板的測試圖案上塗覆焊接膏後，在150℃的熱板上乾燥20秒中。 After the solder paste was applied on the test pattern of the ruthenium substrate and the ITO-deposited glass substrate on which the test pattern was formed, it was dried on a hot plate at 150 ° C for 20 seconds.

接著，在270℃的焊料槽中浸漬3秒鐘後提上來，並從測試圖案的焊料潤濕性(被覆%)對焊接性進行了評價。 Next, it was immersed in a solder bath of 270 ° C for 3 seconds, and then lifted up, and the solderability was evaluated from the solder wettability (cover %) of the test pattern.

將測試圖案上的焊料的被覆面積為100%的作為焊接性非常好來用“○”進行了評價；將測試圖案上的焊料的被覆面積為80%以上且小於100%的作為焊接性良好來用“△”進行了評價；將測試圖案上的焊接的被覆面積為小於80%的作為焊接性差來用“×”進行了評價。這些結果表示在下述第1表裏。另外，相對於矽基板和ITO沉積玻璃基板焊接性都是相同的評價，因此在下述第1表中省略每個基板的評價。 The coating area of the solder on the test pattern was 100%, and the evaluation was evaluated by "○" as the weldability. The coverage of the solder on the test pattern was 80% or more and less than 100%. The evaluation was performed by "△"; the weld coverage area of the test pattern was less than 80%, and the weldability was poor, and it was evaluated by "x". These results are shown in the first table below. In addition, since the weldability was the same as that of the tantalum substrate and the ITO deposited glass substrate, the evaluation of each of the substrates was omitted in the first table below.

第1表中的各成分使用了如下物質。 The following materials were used for each component in the first table.

‧銀粉：AgC-103(形狀：球狀、平均粒徑：1.5μm、福田金屬箔粉工業社製造) ‧ Silver powder: AgC-103 (shape: spherical, average particle size: 1.5 μm, manufactured by Fukuda Metal Foil Powder Co., Ltd.)

‧1,6-雙(三甲氧基甲矽烷基)己烷：KBM-3066(信越化學工業社製造) ‧1,6-bis(trimethoxymethyl decyl) hexane: KBM-3066 (manufactured by Shin-Etsu Chemical Co., Ltd.)

‧1,2-雙(三乙氧基甲矽烷基)乙烷：KBM-6026(信越化學工業社製造) ‧1,2-bis(triethoxycarbenyl)ethane: KBM-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)

‧6-己基三甲氧基矽烷：KBM-3063(信越化學工業社製造) ‧6-Hexyltrimethoxydecane: KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)

‧3-環氧丙氧基丙基三甲氧基矽烷：KBM-403(信越化學工業社製造) ‧3-glycidoxypropyltrimethoxydecane: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

‧雙酚A型環氧樹脂：YD-019(環氧當量：2400~3300g/eq、新日鐵化學社製造) ‧Bisphenol A type epoxy resin: YD-019 (epoxy equivalent: 2400~3300g/eq, manufactured by Nippon Steel Chemical Co., Ltd.)

‧多元醇類縮水甘油醚型環氧樹脂：聚乙二醇二縮水甘油醚(EX-821、環氧當量：185g/eq、Nagase chemteX社製造) ‧Polyol glycidyl ether type epoxy resin: polyethylene glycol diglycidyl ether (EX-821, epoxy equivalent: 185g/eq, manufactured by Nagase ChemteX)

‧固化劑：由上述式(1)表示的芳香族鋶鹽(SI-100L、三新化學工業社製造) ‧ Curing agent: an aromatic sulfonium salt represented by the above formula (1) (SI-100L, manufactured by Sanshin Chemical Industry Co., Ltd.)

‧α-萜品醇：溶劑 ‧α-terpineol: solvent

‧2,2-雙(羥基甲基)-正丁酸銀鹽：首先，將50g氧化銀(東洋化學工業社製造)、64g的2,2-雙(羥基甲基)-正丁酸(東京化成社製造)和300g甲基乙基酮(MEK)投入到球磨機中，並在室溫下攪拌24小時而使其進行反應。接著，通過吸引過濾將MEK去除，通過對所獲得的粉末進行乾燥，由此製造出白色的2,2-雙(羥基甲基)-正丁酸銀鹽。 ‧2,2-bis(hydroxymethyl)-n-butyric acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.) and 64 g of 2,2-bis(hydroxymethyl)-n-butyric acid (Tokyo 300 g of methyl ethyl ketone (MEK) was put into a ball mill, and stirred at room temperature for 24 hours to carry out a reaction. Next, MEK was removed by suction filtration, and the obtained powder was dried to thereby produce a white silver salt of 2,2-bis(hydroxymethyl)-n-butyrate.

‧1,2,3,4-丁烷四羧酸銀鹽：首先，將50g氧化銀(東洋化學工業社製造)、25.29g的1,2,3,4-丁烷四羧酸(新日本理化社製造)和300g甲基乙基酮(MEK)投入到球磨機中，並在室溫下攪拌24小時而使其進行反應。接著，通過吸引過濾將MEK去除，通過對所獲得的粉末進行乾燥，由此製造出白色的1,2,3,4-丁烷四羧酸銀鹽。 ‧1,2,3,4-butanetetracarboxylic acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.) and 25.29 g of 1,2,3,4-butanetetracarboxylic acid (New Japan) 300 g of methyl ethyl ketone (MEK) was put into a ball mill and stirred at room temperature for 24 hours to cause a reaction. Next, MEK was removed by suction filtration, and the obtained powder was dried to thereby produce a white silver salt of 1,2,3,4-butanetetracarboxylic acid.

‧異丁酸銀鹽：首先，將50g氧化銀(東洋化學工業社製造)、38g的異丁酸(關東化學社製造)和300g甲基乙基酮(MEK)投入到球磨機中，並在室溫下攪拌24小時而使其進行反應。接著，通過吸引過濾將MEK去除，通過對所獲得的粉末進行乾燥，由此製造出白色的異丁酸銀鹽。 ‧Isobutyric acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 38 g of isobutyric acid (manufactured by Kanto Chemical Co., Ltd.), and 300 g of methyl ethyl ketone (MEK) were placed in a ball mill and placed in a chamber. The mixture was stirred under heating for 24 hours to cause a reaction. Next, MEK was removed by suction filtration, and the obtained powder was dried to thereby produce a white silver isobutyrate salt.

‧2-羥基異丁酸銀鹽：首先，將50g氧化銀(東洋化學工業社製造)、45g的2-羥基異丁酸(東京化成社製造)和300g甲基乙基酮(MEK)投入到球磨機中，並在室溫下攪拌24小時而使其進行反應。接著，通過吸引過濾將MEK去除，通過對所獲得的粉末進行乾燥，由此製造出白色的2-羥基異丁酸銀鹽。 ‧2-Hydroxyisobutyric acid silver salt: First, 50 g of silver oxide (manufactured by Toyo Chemical Co., Ltd.), 45 g of 2-hydroxyisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 300 g of methyl ethyl ketone (MEK) are put into The mixture was stirred in a ball mill and allowed to react at room temperature for 24 hours. Next, MEK was removed by suction filtration, and the obtained powder was dried to thereby produce a white silver 2-hydroxyisobutyrate salt.

從第1表中所示的結果中可知，使用僅具有一個氧烷基甲矽烷基的矽烷化合物製造出的比較例1和比較例2的導電性組成物，雖然其體積阻抗率低，但與沒有使用矽烷化合物製造出的比較例3的導電性組成物相比，提高剪切剝離強度的效果幾乎看不到，並且可知與矽基板和ITO沉積玻璃基板的黏著性差。 From the results shown in Table 1, it is understood that the conductive compositions of Comparative Example 1 and Comparative Example 2 produced using a decane compound having only one oxyalkylcarbenyl group have a low volume resistivity, but The effect of improving the shear peel strength was hardly observed compared to the conductive composition of Comparative Example 3 which was produced without using a decane compound, and it was found that the adhesion to the ruthenium substrate and the ITO-deposited glass substrate was inferior.

相對於此，可知使用具有兩個以上氧烷基甲矽烷基的 規定的矽烷化合物製造出的實施例1~9的導電性組成物體積阻抗率低，且相對於矽基板和ITO沉積玻璃基板的黏著性優異。 In contrast, it is known that two or more oxyalkylcarbenyl groups are used. The conductive compositions of Examples 1 to 9 produced by the predetermined decane compound had a low volume resistivity and were excellent in adhesion to the ruthenium substrate and the ITO-deposited glass substrate.

尤其是，可知相對於100質量份的銀粉，混合0.1~0.5質量份的矽烷化合物而製造出的實施例1~3和實施例6~9的導電性組成物體積阻抗率和相對於矽基板和ITO沉積玻璃基板的黏著性的均衡性優異。 In particular, it is known that the volume resistivity of the conductive compositions of Examples 1 to 3 and Examples 6 to 9 which were produced by mixing 0.1 to 0.5 parts by mass of a decane compound with respect to 100 parts by mass of the silver powder, and the ruthenium substrate and The ITO deposited glass substrate is excellent in the balance of adhesion.

另外，可知同時使用規定範圍內的環氧當量的雙酚A型環氧樹脂和多元醇類縮水甘油醚型環氧樹脂製造出的實施例1~6和實施例8和實施例9的導電性組成物，其焊接性也非常好。 Further, it is understood that the electrical conductivity of Examples 1 to 6 and Examples 8 and 9 produced by using a bisphenol A type epoxy resin and a polyol type glycidyl ether type epoxy resin having an epoxy equivalent in a predetermined range at the same time. The composition also has excellent weldability.

進一步，可知使用分別具有一個以上羧基銀鹽基(-COOAg)和羥基(-OH)的脂肪酸銀鹽或者具有三個以上羧基銀鹽基(-COOAg)的聚羧酸銀鹽製造出的實施例1~7和實施例9的導電性組成物時，體積阻抗率低，且相對於矽基板和ITO沉積玻璃基板的黏著性更優異。 Further, it is understood that the examples produced by using a silver salt of a fatty acid having one or more carboxylated silver salt groups (-COOAg) and a hydroxyl group (-OH) or a silver salt of a polycarboxylic acid having three or more carboxyl silver salt groups (-COOAg) In the conductive compositions of 1 to 7 and Example 9, the volume resistivity was low, and the adhesion to the tantalum substrate and the ITO-deposited glass substrate was more excellent.

1‧‧‧太陽能電池單元 1‧‧‧Solar battery unit

2‧‧‧表面電極 2‧‧‧ surface electrode

3‧‧‧透明導電氧化膜(TCO) 3‧‧‧Transparent Conductive Oxide Film (TCO)

4‧‧‧p型非晶矽層 4‧‧‧p-type amorphous germanium layer

5‧‧‧i型非晶矽層 5‧‧‧i type amorphous layer

6‧‧‧n型非晶矽層 6‧‧‧n type amorphous layer

7‧‧‧矽基板 7‧‧‧矽 substrate

8‧‧‧背面電極 8‧‧‧Back electrode

9‧‧‧塑膠薄膜基板 9‧‧‧Plastic film substrate

10‧‧‧保護薄膜 10‧‧‧Protective film

11‧‧‧環氧類黏結劑 11‧‧‧Epoxy adhesive

12‧‧‧測試片 12‧‧‧Test piece

13‧‧‧測試圖案(導電性組成物) 13‧‧‧Test pattern (conductive composition)

14‧‧‧矽基板或ITO沉積玻璃基板 14‧‧‧矽 substrate or ITO deposited glass substrate

15‧‧‧不銹鋼板 15‧‧‧Stainless steel plate

圖1為表示太陽能電池單元的優選實施方式的一個例子的截面圖；圖2為說明用於黏著性評價的剪切測試片的側視圖。 1 is a cross-sectional view showing an example of a preferred embodiment of a solar cell unit; and FIG. 2 is a side view illustrating a shear test piece for evaluation of adhesion.

Claims (13)

一種太陽能電池集電電極形成用導電性組成物，其特徵為，含有銀粉(A)與下述式(I)所表示之矽烷化合物(B)， (式中，R1和R2分別獨立表示烷基，R3表示可以具有雜原子的2價烷烴，m表示1~3的整數，複數之R1與R2分別可為相同亦可為不同)。 A conductive composition for forming a current collector electrode for a solar cell, comprising: a silver powder (A) and a decane compound (B) represented by the following formula (I); (wherein R 1 and R 2 each independently represent an alkyl group, R 3 represents a divalent alkane which may have a hetero atom, m represents an integer of 1 to 3, and a plurality of R 1 and R 2 may be the same or different ). 如請求項1之太陽能電池集電電極形成用導電性組成物，其中，上述銀粉(A)之至少一部分為平均粒徑0.5~10μm之球狀銀粉末。 The conductive composition for forming a solar cell collecting electrode according to claim 1, wherein at least a part of the silver powder (A) is a spherical silver powder having an average particle diameter of 0.5 to 10 μm. 如請求項1或2之太陽能電池集電電極形成用導電性組成物，其中，上述矽烷化合物(B)係於上述式(I)中，R1與R2分別獨立地表示甲基或乙基，R3表示碳數為2~10之伸烷基，m表示2或3。 The conductive composition for forming a solar cell collector electrode according to claim 1 or 2, wherein the decane compound (B) is in the above formula (I), and R 1 and R 2 each independently represent a methyl group or an ethyl group. R 3 represents an alkylene group having a carbon number of 2 to 10, and m represents 2 or 3. 如請求項1或2之太陽能電池集電電極形成用導電性組成物，其中，相對於100質量份之上述銀粉(A)，上述矽烷化合物(B)之含有量為0.05~1.0質量份。 The conductive composition for forming a solar cell collecting electrode according to claim 1 or 2, wherein the content of the decane compound (B) is 0.05 to 1.0 part by mass based on 100 parts by mass of the silver powder (A). 如請求項1或2之太陽能電池集電電極形成用導電性組成物，其中，進而含有環氧樹脂(C)。 The conductive composition for forming a solar cell current collector according to claim 1 or 2, further comprising an epoxy resin (C). 如請求項1或2之太陽能電池集電電極形成用導電 性組成物，其中，進而含有脂肪酸銀鹽(D)。 Solar cell collector electrode forming conductive material according to claim 1 or 2 The sexual composition further contains a fatty acid silver salt (D). 如請求項5之太陽能電池集電電極形成用導電性組成物，其中，上述環氧樹脂(C)至少是環氧當量為1500~4000g/eq之雙酚A型環氧樹脂(C1)及環氧當量為1000g/eq以下之多元醇類縮水甘油醚型環氧樹脂(C2)。 The conductive composition for forming a solar cell collector electrode according to claim 5, wherein the epoxy resin (C) is at least a bisphenol A type epoxy resin (C1) and a ring having an epoxy equivalent of 1500 to 4000 g/eq. A polyol glycidyl ether type epoxy resin (C2) having an oxygen equivalent of 1000 g/eq or less. 如請求項6之太陽能電池集電電極形成用導電性組成物，其中，上述脂肪酸銀鹽(D)為分別具有1個以上羧基銀鹽基(-COOAg)與羥基(-OH)之脂肪酸銀鹽(D1)及/或具有3個以上羧基銀鹽基(-COOAg)之聚羧酸銀鹽(D2)。 The conductive composition for forming a solar cell current collector electrode according to claim 6, wherein the fatty acid silver salt (D) is a fatty acid silver salt having one or more carboxyl silver salt groups (-COOAg) and a hydroxyl group (-OH), respectively. (D1) and/or a polycarboxylic acid silver salt (D2) having three or more carboxylated silver salt groups (-COOAg). 如請求項8之太陽能電池集電電極形成用導電性組成物，其中，上述脂肪酸銀鹽(D1)為2,2-雙(羥基甲基)-正丁酸銀鹽及/或2-羥基異丁酸銀鹽。 The conductive composition for forming a solar cell collector electrode according to claim 8, wherein the fatty acid silver salt (D1) is a 2,2-bis(hydroxymethyl)-n-butyric acid silver salt and/or a 2-hydroxy group. Silver butyrate salt. 如請求項8之太陽能電池集電電極形成用導電性組成物，其中，上述聚羧酸銀鹽(D2)為1,2,3,4-丁烷四羧酸銀鹽。 The conductive composition for forming a solar cell collector electrode according to claim 8, wherein the polycarboxylate silver salt (D2) is a 1,2,3,4-butanetetracarboxylic acid silver salt. 如請求項5之太陽能電池集電電極形成用導電性組成物，其中，相對於100質量份之上述銀粉(A)，上述環氧樹脂(C)之含有量為2~20質量份。 The conductive composition for forming a solar cell collector electrode according to claim 5, wherein the content of the epoxy resin (C) is 2 to 20 parts by mass based on 100 parts by mass of the silver powder (A). 如請求項6之太陽能電池集電電極形成用導電性組成物，其中，相對於100質量份之上述銀粉(A)，上述脂肪酸銀鹽(D)之含有量為0.1~10質量份。 The conductive composition for forming a solar cell collecting electrode according to claim 6, wherein the content of the fatty acid silver salt (D) is 0.1 to 10 parts by mass based on 100 parts by mass of the silver powder (A). 一種太陽能電池單元，其特徵為，具有受光面側之表面電極、半導體基板以及背面電極，且使用請求項1 或2之太陽能電池集電電極形成用導電性組成物形成上述表面電極及/或上述背面電極。 A solar battery cell characterized by having a surface electrode on a light receiving surface side, a semiconductor substrate, and a back surface electrode, and using claim 1 Or the solar cell current collecting electrode forming conductive composition forms the surface electrode and/or the back surface electrode.
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